WO2015135402A1 - 珠光颜料的制备方法及应用 - Google Patents

珠光颜料的制备方法及应用 Download PDF

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WO2015135402A1
WO2015135402A1 PCT/CN2015/072234 CN2015072234W WO2015135402A1 WO 2015135402 A1 WO2015135402 A1 WO 2015135402A1 CN 2015072234 W CN2015072234 W CN 2015072234W WO 2015135402 A1 WO2015135402 A1 WO 2015135402A1
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inorganic substance
water
weight
coating
parts
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PCT/CN2015/072234
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English (en)
French (fr)
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谢秉昆
曹志成
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福建坤彩材料科技股份有限公司
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Priority to KR1020167027520A priority Critical patent/KR102038917B1/ko
Priority to US15/124,538 priority patent/US10287437B2/en
Priority to DE112015001175.7T priority patent/DE112015001175B9/de
Publication of WO2015135402A1 publication Critical patent/WO2015135402A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation
    • C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Definitions

  • This invention relates to a process for the preparation of pearlescent pigments, and more particularly to a process for the preparation of pearlescent pigments free of free particles.
  • the bases mentioned above are all water-soluble and are generally prepared as an aqueous solution in production and then added to the reaction vessel. Even if the above water-soluble base is added in a solid form, once it enters the reaction vessel, it dissolves into a solution while providing the desired hydroxide (OH - ) to neutralize the acid (H + ) for the purpose of controlling the stable pH.
  • This process has a drawback: when the base enters the reaction vessel, the concentration of the local alkali is inevitably formed too high, and the local high-concentration alkali (OH - ), in addition to neutralizing the acid, also forms a metal ion for the coating.
  • the present invention provides a new technique for pH control using a water-insoluble substance, completely avoiding the direct reaction of a base with a metal ion, thereby preparing a pearlescent pigment free of free particles. Since the substance added to the reaction vessel for neutralizing the acid is insoluble in water, OH - is not directly supplied, and the local concentration of the alkali (OH - ) is prevented from being excessively high, and the substance neutralizing the acid (such as MgO) is used only. Reacts with an acid (H + ) to react with a different metal ion (such as TiO 2+ ).
  • the salt formed by the reaction of the water-insoluble matter (e.g., MgO) with the acid (e.g., MgCl 2 ) is soluble in water and thus removed in the subsequent filtration washing, thereby producing a high-quality pearlescent pigment free of free particles.
  • the water-insoluble matter e.g., MgO
  • the acid e.g., MgCl 2
  • a method of preparing a pearlescent pigment comprising: A) setting in the presence of a sheet-like substrate and in a state in which a metal salt for a coating can be hydrolyzed At a pH value, a hydrolysis coating is carried out by simultaneously adding a metal salt for coating in water and an inorganic substance insoluble in water but capable of reacting with an acid, wherein the inorganic substance is used to adjust or maintain the pH of the hydrolysis system.
  • the metal salt is used in an amount of from 350 to 1,500 parts by weight, preferably from 450 to 1350 parts by weight, based on 1000 parts by weight of the sheet-form substrate, and the inorganic substance is used in an amount of from 300 to 1400 parts by weight, preferably from 400 to 1200 parts by weight.
  • the sheet-form substrate is preferably used in the form of a water slurry having a solid weight of 5 to 30% by weight, preferably 10 to 15% by weight.
  • the particle diameter of the sheet substrate is preferably from 10 to 60 ⁇ m.
  • the thickness of the coating formed is generally from 10 to 100 nm, preferably from 30 to 60 nm, more preferably from 40 to 50 nm.
  • the set pH as described above is in the range of 0.5 to 3, preferably in the range of 0.7 to 2.5, more preferably in the range of 0.8 to 2, still more preferably in the range of 0.9 to 1.5 (e.g., 1, 1.1, 1.2 or 1.3). .
  • the inorganic substance which is insoluble in water but which is soluble in the reaction with an acid is an alkaline earth metal compound, more preferably an oxide or carbonate of an alkaline earth metal.
  • the inorganic substance is preferably used in the form of an aqueous solution or slurry of 5 to 30% by weight, more preferably 10 to 20% by weight.
  • the particle diameter of the inorganic substance is preferably 200 mesh or less, preferably 200 to 250 mesh or 200 to 300 mesh.
  • the above described method further comprises the steps of: B) filtration, C) washing, D) drying and E) calcination.
  • the metal salt for the coating is added in the form of an aqueous solution; and/or the inorganic substance which is insoluble in water but capable of reacting with the acid to be dissolved is added in the form of a slurry or slurry formed in water.
  • the metal salt is preferably used in a concentration of from 1 to 4 mol/liter, preferably from 1.5 to 3 mol/liter.
  • the rate of addition of the inorganic substance which is insoluble in water but which is soluble in the reaction with the acid is controlled in step A) such that the pH of the hydrolysis system remains stable or substantially stable.
  • the sheet-form substrate used in the present invention is one or two or more selected from the group consisting of natural mica, synthetic mica, glass flakes, flake alumina, and flake metals.
  • the metal salt for the coating used in the present invention is one or two or more selected from the group consisting of TiCl 4 , TiOCl 2 , FeCl 3 or SnCl 4 .
  • the above inorganic substance is selected from the group consisting of magnesium oxide, magnesium hydroxide, calcium carbonate or a mixture thereof.
  • the coating material is calcined to be one of the following: anatase TiO 2 , tin dioxide SnO 2 , rutile TiO 2 , hematite Fe 2 O 3 , TiO 2 +FeO 3 , SnO 2 + TiO 2 + Fe 2 O 3 , SnO 2 + Fe 2 O 3 , a mixed oxide of titanium and iron, and a mixed oxide of tin, titanium, and iron.
  • the amount of the metal salt and the amount of the inorganic substance can be determined according to the color to be coated, for example, in the case where the inorganic substance is MgO and the metal salt is TiCl 4 , if the product color is silver white, relative to 1000 parts by weight of the sheet substrate
  • the inorganic substance is 370 to 430 parts by weight, for example, 400 parts by weight, and the metal salt is 420 to 480 parts by weight.
  • the color of the product ranges from golden, red, blue to green, and the amount of inorganic and metal salts increases in turn.
  • the inorganic substance is 1100 to 1300 parts by weight and the metal salt is 1300 to 1400 parts by weight with respect to 1000 parts by weight of the sheet substrate.
  • a pearl pigment obtained by the above method is provided.
  • the use of the above pearlescent pigments is provided for use in the fields of paints, printing inks, plastics, ceramic materials, leather coloring, wallpaper, powder coatings or cosmetics.
  • the pearlescent pigments produced by the present invention contain almost no free particles. Good quality, excellent color and finish.
  • Fig. 1 is a view showing a case where a sample of a hydrolyzed coating slurry prepared by a new process (left) of the present invention and a conventional process (right) is placed in a glass bottle and settled statically for a certain period of time.
  • the titanium liquid pump and the MgO slurry pump are simultaneously activated, and the pH is automatically controlled to 1.0 by a pH meter.
  • the titanium liquid used is prepared by adding TiCl 4 with a purity of not less than 99%, and the amount of water is generally 1:1 with the amount of TiCl 4 , and is prepared into a titanium tetrachloride solution having a concentration of 2 mol/liter, and HCl gas is generated when diluted. .
  • Hydrochloric acid is obtained by absorbing the released HCl gas with water. In order to keep the diluted TiCl 4 from hydrating and deteriorating, it is necessary to add a sufficient amount of hydrochloric acid.
  • the amount of TiCl 4 solution determines the final product is golden yellow, orange, red, purple, blue, green, and the like.
  • the brightness and chromaticity of the product obtained by the novel process of the invention are significantly improved, and the water consumption during filtration washing is saved by more than half. . This indicates that the new process does not produce free particles during hydrolysis, so filtration washing is easier and the quality of the resulting product is better.
  • Another method for indicating that the product obtained by the new process does not contain free particles is that the sample of the hydrolyzed coating slurry prepared by the new process and the conventional process is separately placed in a glass bottle, and after a certain period of static sedimentation, the new process
  • the upper mother liquor (left side) of the prepared hydrolyzed coating slurry sample was significantly more transparent than the upper mother liquor of the conventional process sample (see Figure 1).
  • the upper mother liquor of the dispersion of the present invention is transparent, while the upper mother liquor of the prior art dispersion is cloudy.
  • the sample quality is evaluated by the common method of coating or spraying the board: a certain amount of pearl powder sample ( ⁇ 10%) is added to the resin or paint, coated by filming or sprayed, and dried. .
  • the resulting product was a pearlescent powder without free TiO 2 .
  • mice and MgO slurry were prepared as described in Example 1 and the pH was adjusted to 3.0.
  • An additional 10% FeCl 3 solution was prepared: 1000 kg FeCl 3 was dissolved in 9000 liters of deionized water. While the pump was added a solution of FeCl 3 and MgO slurry, and automatically control the PH of 3.0. After an appropriate amount of FeCl 3 solution is added to the reaction vessel, the pearlescent powder having a metallic luster is obtained by filtration, washing, and calcination. The amount of FeCl 3 solution determines the final product as gold, orange, red, purple, green, and the like. Taking brass gold products as an example, the amount of mica, MgO, FeCl 3 is 1000:400:400 (kg) by dry weight. The film thus formed had a thickness of 50 nm.
  • the mica slurry was prepared in the same manner as in Example 2, and a SnO 2 coating was carried out, and then an iron coating was carried out in the same manner as in Example 3 at a pH of 3.0.
  • the pearlescent powder with metallic luster is obtained by filtration, washing and calcination.
  • the amount of FeCl 3 solution determines the final product as gold, orange, red, purple, green, and the like.
  • the actual amounts of mica, ferric chloride (not titanium tetrachloride) and MgO, SnCl 4 are respectively 1000:400:400:10 (kg).
  • the resulting film has a thickness of about 50 nm.
  • the titanium was coated in the same manner as in Example 1 and then the pH was adjusted to 3.0, and the iron coating was carried out as described in Example 3. After filtering, washing and calcining, a pearlescent powder with a metallic luster of titanium and iron is coated. The ratio of titanium to iron and the amount used determine the color of the final product.
  • a titanium iron 2-layer coated pearlescent pigment was obtained by coating the titanium coating of Example 2 with the iron coating of Example 3.
  • Example 7 A tin coating film was applied as in Example 2, and a titanium-iron mixed coating was carried out as in Example 7.
  • the envelopes of Examples 1-8 were repeated except that the sheet substrate was synthetic mica.
  • Example 9 was repeated except that the sheet substrate was a glass piece.
  • Example 9 was repeated, and the sheet substrate was alumina.
  • Example 9 was repeated except that the sheet substrate was a metal sheet of Al, Cu, Ni, and various alloys.
  • Examples 1-12 were repeated except that the pH control agent MgO slurry could be replaced with a Mg(OH) 2 slurry, or a mixture of MgO slurry and Mg(OH) 2 slurry.
  • Example 13 was repeated except that the pH control agent may be a mixture of calcium carbonate (CaCO 3 ) or CaCO 3 /MgO/Mg(OH) 2 in any ratio.
  • the pH control agent may be a mixture of calcium carbonate (CaCO 3 ) or CaCO 3 /MgO/Mg(OH) 2 in any ratio.
  • the pearlescent pigments obtained in the above Examples 1-14 are used in applications such as paints, coatings, printing inks, plastics, ceramic materials, leather coloring, wallpapers, powder coatings, cosmetics, and the like.
  • applications such as paints, coatings, printing inks, plastics, ceramic materials, leather coloring, wallpapers, powder coatings, cosmetics, and the like.
  • by adding the pearlescent pigment of the present invention to a paint or a coating it is possible to prepare a coating excellent in color and color.
  • the analytical scale was prepared to weigh 4.000 g of pearl powder into a plastic sealed bag, shake it again, and ⁇ , so that the pearl powder was uniformly and uniformly dispersed in the PP particles.
  • the prepared polypropylene material is added into the hopper, and the original residual material in the barrel is extruded by using the glue and melt glue function until the new material is extruded. So far, the new material should be shiny, no impurities, no black spots, no charring, no bubbles; at the same time, the nozzle should be free of blockage when shooting. After the two pieces of plastic sheets are not different, the plastic sheets produced are stable and qualified products, and can enter automatic normal production.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及基于片状基材的通过金属氧化物包膜来制备珠光颜料的方法和所得珠光颜料。本发明还涉及由金属盐在酸性条件下水解来包覆片状基材以便制备珠光颜料的方法，其中使用不溶于水但能够与酸反应而溶解的无机物如MgO、MgOH或CaCO3等来调节pH。所述方法在进行金属盐的水解时不产生游离状态的金属氧化物，从而节省了生产成本，提高了产品品质，避免了产品在应用过程中可能出现的问题，并且使生产工艺更加环保。

Description

珠光颜料的制备方法及应用 技术领域
本发明涉及制备珠光颜料的方法，尤其涉及制备没有游离颗粒的珠光颜料的方法。
背景技术
以片状材料为基材、单层或多层氧化物包膜来制备具有珠光效果的颜料已经有几十年的历史，工艺很成熟，并已经有大量的文献专利，其中通过水溶性金属盐在预先设定的PH值下进行强制水解包膜是最常用的工艺之一，因为水溶性金属盐通常为酸性，在连续加入时，必须同时加入碱来恒定PH值，否则水解无法持续进行。目前用来中和酸和碱主要是金属氢氧化物，如NaOH,KOH等。使用氨水(NH3●H2O)或碳酸钠(Na2CO3)等也能控制PH值，进行水解包膜。以上所提到的碱均为水溶性，并在生产中一般先制成水溶液，然后加到反应釜中。即使上述水溶性碱以固体形式加入，一旦进入反应釜便溶解变成溶液，同时提供所需的氢氧根(OH-)来中和酸(H+)，以达到控制稳定PH值的目的。这种工艺有一个缺陷：当碱进入到反应釜时，不可避免地形成局部碱的浓度过高，局部的高浓度碱(OH-)除了中和酸以外，还会和包膜所用的金属离子(如：Ti4+、TiO2+、Fe3+、Sn4+等)结合，生产金属氢氧化物(或水合金属氧化物)沉淀，并且没有完全包覆在片状基材上而形成游离。这些游离物因为尺寸小(通常为纳米级)，比表面积大，具有较强的吸附能力，因而导致后续的水解包膜在这些游离颗粒和片状基材间互相竞争。一旦形成这种游离颗粒，只有靠后面的过滤，洗涤，气流分级等各步骤来除去，因为游离的颗粒会严重降低珠光颜料的色度，并给应用带来各种问题。虽然通过搅拌，加料速度等的严格控制能够减少游离颗粒的形成，但上述工艺不能从根本上消除游离颗粒的形成。
发明内容
本发明提供了一种新技术，采用不溶于水的物质来进行PH控制，完全避免了碱同金属离子的直接反应，从而制备出没有游离颗粒的珠光颜料。因为加入到反应釜中用来中和酸的物质不溶于水，因此不直接提供OH-，避免了碱(OH-)的局域浓度过高现象，所用中和酸的物质(如MgO)只与酸(H+)反应而不同金属离子(如TiO2+)反应。不溶于水的物质(如MgO)与酸反应后所生成的盐(如MgCl2)可溶于水，因此在后续的过滤洗涤中被除去，从而制得了无游离颗粒的高品质的珠光颜料。
因此，根据本发明的第一个实施方案，提供一种制备珠光颜料的方法，该方法包括：A)在片状基材的存在下和在使得包膜用的金属盐能够发生水解的设定pH值下，通过在水中同时添加包膜用的金属盐和不溶于水但能够与酸反应而溶解的无机物进行水解包膜，其中所述无机物用于调节或维持该水解体系的pH值。
优选地，相对于1000重量份片状基材，金属盐的用量为350～1500重量份，优选450～1350重量份，无机物的用量为300～1400重量份，优选400～1200重量份。所述片状基材优选以固体重量5～30wt％，优选10～15wt％的水浆液的形式使用。片状基材的粒径优选为10～60微米。水解包膜后，所形成的包膜厚度一般为10～100nm，优选30～60nm，更优选40～50nm。
优选地，以上所述的设定pH是在0.5-3范围，优选在0.7-2.5范围，更优选在0.8-2范围，仍然更优选在0.9-1.5(例如1、1.1、1.2或1.3)范围。
优选的是，不溶于水但能够与酸反应而溶解的无机物是碱土金属化合物，更优选是碱土金属的氧化物或碳酸盐。无机物优选以5～30重量％，更优选10～20重量％的水溶液或浆液的形式使用。无机物的粒径优选为200目以下，优选200～250目或200～300目。
一般来说，以上所述的方法进一步包括以下步骤：B)过滤、C)洗涤、D)烘干和E)煅烧。
优选的是，包膜用的金属盐是以水溶液的形式添加；和/或，其中不溶于水但能够与酸反应而溶解的无机物是以在水中形成的淤浆形式或浆液的形式添加。金属盐优选以1～4摩尔/升，优选1.5～3摩尔/升的浓度使用。
优选的是，在步骤A)中控制所述不溶于水但能够与酸反应而溶解的无机物的添加速率，使得水解体系的pH值维持稳定或基本上稳定。
优选的是，用于本发明中的片状基材是选自于天然云母，合成云母，玻璃片，片状氧化铝，和片状金属中的一种或两种或多种。
优选的是，用于本发明中的包膜用的金属盐是选自于TiCl4、TiOCl2、FeCl3或SnCl4中的一种或两种或多种。
进一步优选的是，上述无机物选自：氧化镁、氢氧化镁、碳酸钙或它们的混合物。
优选的是，包膜材料经煅烧后成为下列中的一种：锐钛矿型TiO2，二氧化锡SnO2，金红石型TiO2，赤铁矿型Fe2O3，TiO2+FeO3，SnO2+TiO2+Fe2O3，SnO2+Fe2O3，钛和铁的混合氧化物，以及锡、钛、铁的混合氧化物。
金属盐的用量和无机物的用量可根据所要包覆的颜色来确定，例如在无机物为MgO、 金属盐为TiCl4的情况下，如果产品颜色为银白，相对于1000重量份片状基材，无机物为370～430重量份，例如400重量份，金属盐为420～480重量份。以下，产品颜色从金黄、红、蓝到绿，无机物和金属盐的用量依次递增。例如产品为绿色时，相对于1000重量份片状基材，无机物为1100～1300重量份，金属盐为1300～1400重量份。
根据本发明的第二个实施方案，提供由上述方法所获得的珠光颜料。
根据本发明的第三个实施方案，提供上述珠光颜料的用途，它用于油漆、印刷油墨、塑料、陶瓷材料、皮革着色、壁纸、粉末涂料或化妆品领域。
本发明的优点：
本发明制得的珠光颜料几乎不含游离颗粒。品质好，色泽和光洁度都非常理想。
附图说明
图1是本发明新工艺(左)与传统工艺(右)制备的水解包膜浆料样品分别放置于玻璃瓶中,静止沉降一定时间后的情况。
具体实施方式
以下实施例用于更具体描述本发明而非限定。
实施例1
1000kg天然云母片，粒径为D10＝10μm，D50＝25μm，D90＝60μm，加入到10000升去离子水中，反应釜为20000升，搅拌加热到80℃，用1:1的盐酸调节PH值为1.0，另外配置MgO浆料：1000kg 99％的MgO加入到5000升水中，搅拌，配置为总固体浓度20％的浆料。为了使所配制的浆液不沉降，选用粒径小于200目。开始水解包膜时，同时开动钛液泵和MgO浆液泵，并用PH计自动控制PH为1.0。所用钛液是用纯度不小于99％的TiCl4加水配制，一般加水的量与TiCl4的量为1:1，调制为浓度2摩尔/升的四氯化钛溶液，稀释时会产生HCl气体。用水吸收释放出的HCl气体获得盐酸。为保持稀释后的TiCl4不发生水解变质，需要加入足够量的盐酸。通过同时泵加钛液和MgO浆料到反应釜中，PH恒定在1.0，所加钛液在PH＝1.0时不断水解包膜在云母基材上，经过滤、洗涤、煅烧制得银白及虹彩等珠光产品。TiCl4溶液的用量决定了最终产品为金黄色、橙色、红色、紫色、蓝色、绿色等。
Figure PCTCN2015072234-appb-000001
与传统工艺(用氢氧化钠等碱溶液控制水解薄膜的PH值)相比，此发明的新工艺所制得的产品亮度及色度均有明显提高，并且过滤水洗时的用水量节省一半以上。这都表明新工艺在水解时不产生游离微粒,因此过滤水洗更容易,所得产品的品质更好。
另外一种表明新工艺所制得的产品不含有游离微粒的方法是:将新工艺与传统工艺所制得的水解包膜浆料样品分别放置于玻璃瓶中,静止沉降一定时间后,新工艺所制得的水解包膜浆料样品上部母液(左面)明显较传统工艺的样品上部母液更透明(见附图1)。从附图1中可以看出，本发明的分散体的上层母液是透明的，而现有技术的分散体的上层母液是浑浊的。
样品质量的评估采用常见的涂布划卡或喷板的方法是:将一定量的珠光粉样品(～10％)加入到树脂或油漆中,经涂布划卡或喷板成膜,烘干。用X-Rite MA68色差仪测量色泽和光洁度数据。数据以CIE L*,a*,b*体系展示。L*数值代表亮度，c值(c2＝a2+b2)代表色泽浓度。
实施例2
按实施例1所述方法制备云母浆，钛液及MgO浆，另外再制备20％的SnCl4溶液：10kgSnCl4溶于40kg去离子水中，泵加入PH＝1.0的反应釜中，然后按实施例1所述进行钛包膜，并用MgO浆液自动控制PH为1.0。达到所要的颜色后经过滤、洗涤、烘干、煅烧制得产品，以银白色产品为例，云母，99％的TiCl4，SnCl4和MgO重量分别为：1000： 450：10：400(kg)。最终所形成的膜的厚度为45纳米。
所得产品为没有游离TiO2的珠光粉。
实施例3：
按实施例1所述制备云母浆和MgO浆，并调节PH至3.0。另外制备10％的FeCl3溶液：1000kg FeCl3溶于9000升的去离子水中。同时泵加FeCl3溶液和MgO浆，并自动控制PH为3.0。当适量的FeCl3溶液加入反应釜后，经过滤、洗涤、煅烧制得具有金属光泽的珠光粉。FeCl3溶液的量决定了最终产品为金色、橙色、红色、紫色、绿色等。以黄铜金色产品为例，云母、MgO、FeCl3的用量按干重计分别为：1000：400：400(kg)。最终所形成的膜的厚度为50纳米。
实施例4：
按实施例2方式制备云母浆并进行SnO2包膜，然后将PH值至3.0按实施例3方式进行铁包膜。经过滤、洗涤、煅烧制得具有金属光泽的珠光粉。FeCl3溶液的量决定了最终产品为金色、橙色、红色、紫色、绿色等。以黄铜金色产品为例，云母、三氯化铁(不是四氯化钛)和MgO、SnCl4的实际用量分别1000：400：400：10(kg)。最终所形成的膜的厚度约为50纳米。
实施例5：
按实施例1方式包钛后再将PH值至3.0，按实施例3所述进行铁包膜。经过滤、洗涤、煅烧制得具有金属光泽的钛、铁2层包膜的珠光粉。钛、铁比例及用量决定最终产品的颜色。
实施例6：
按实施例2的钛包膜后再按实施例3的铁包膜制得钛铁2层包膜的珠光颜料。
实施例7：
将实施例1中的钛液与实施例3中的铁液按Ti:Fe＝100:10(重量比)比例混合，并按实施例1制备云母浆调PH值至2.5，用MgO浆自动控制PH为2.5进行钛铁混合包膜。
实施例8：
按实施例2进行锡包膜，再按实施例7进行钛铁混合包膜。
实施例9：
重复实施例1-8的包膜，只是片状基材为合成云母。
实施例10：
重复实施例9，只是片状基材为玻璃片。
实施例11：
重复实施例9，片状基材为氧化铝。
实施例12：
重复实施例9，只是片状基材为Al、Cu、Ni及各种合金的金属片。
实施例13：
重复实施例1-12，只是PH控制剂MgO浆可以换为Mg(OH)2浆，或MgO浆和Mg(OH)2浆的混合物。
实施例14：
重复实施例13，只是PH控制剂可以用碳酸钙(CaCO3)浆或CaCO3/MgO/Mg(OH)2，按任意比例的混合物。
应用实施例
以上实施例1-14所制得的珠光颜料用于油漆、涂料、印刷油墨、塑料、陶瓷材料、皮革着色、壁纸、粉末涂料、化妆品等应用领域。例如在油漆或涂料中添加本发明的珠光颜料，能够制备色彩和色泽非常优异的涂层。
应用实施例1：以油漆喷涂应用为例:
准确称量4.00克珠光颜料，添加4.0克醋酸丁酯及8.0克聚酯汽车涂料树脂，置于搅拌器下搅拌分散10分钟，继续添加汽车涂料树脂体系84.0克搅拌5分钟。喷涂前先调整涂料的黏度至Ford 4号杯14-15秒。喷涂时控制喷涂间的温度为25摄氏度，相对湿度为60％。喷涂两遍，闪干10分钟后罩清漆，再次闪干后于140摄氏度烘烤30分钟。
应用实施例2：以注塑应用为例:
准确称取200克105℃下干燥过的聚丙烯(PP)料于塑料密封袋中，加入1毫升的光油(也叫分散油)然后振荡，让光油与聚丙烯料充分混合。
用分析天平准备称取4.000克的珠光粉加入塑料密封袋中，再次振荡，揉搓，使珠光粉充分均匀分散在PP颗粒中。
料筒温度达到设定值后(通常为180℃～200℃)，把配好的聚丙烯料加入料斗里面，使用射胶和熔胶功能把料筒内原有余料挤出，直到挤出新料为止，挤出新料应有光泽，无杂质、无黑点、无烧焦、无气泡；同时，射胶时喷嘴应无堵塞现象。待出来的塑料片前后两片无异后，再生产出来的塑料片即为稳定合格的产品，可以进入自动的正常生产。

Claims (10)

  1. 制备珠光颜料的方法，该方法包括：A)在片状基材的存在下和在使得包膜用的金属盐能够发生水解的设定pH值下，通过在水中同时添加包膜用的金属盐和不溶于水但能够与酸反应而溶解的无机物进行水解包膜，其中所述无机物用于调节或维持该水解体系的pH值。
  2. 根据权利要求1的方法，其中相对于1000重量份片状基材，金属盐的用量为350～1500重量份，优选450～1350重量份，无机物的用量为300～1400重量份，优选400～1200重量份。
  3. 根据权利要求1的方法，其中该设定pH是在0.5-3范围，优选在0.7-2.5范围，更优选在0.8-2范围，仍然更优选在0.9-1.5(例如1或1.3)范围。
  4. 根据权利要求1-3中任何一项的方法，其中不溶于水但能够与酸反应而溶解的无机物是碱土金属化合物，优选是碱土金属的氧化物或碳酸盐。
  5. 根据权利要求1-4中任何一项的方法，其中所述方法进一步包括以下步骤：B)过滤、C)洗涤、D)烘干和E)煅烧。
  6. 根据权利要求1-5中任何一项的方法，其中包膜用的金属盐是以水溶液的形式添加；和/或，其中不溶于水但能够与酸反应而溶解的无机物是以在水中形成的淤浆形式或浆液的形式添加；优选地，在步骤A)中控制所述不溶于水但能够与酸反应而溶解的无机物的添加速率，使得水解体系的pH值维持稳定或基本上稳定。
  7. 根据权利要求1-6中任何一项的方法，其中片状基材是选自于天然云母，合成云母，玻璃片，片状氧化铝，和片状金属中的一种或两种或多种；和/或
    包膜用的金属盐是选自于TiCl4、TiOCl2、FeCl3或SnCl4中的一种或两种或多种；和/或所述无机物选自：氧化镁、氢氧化镁、碳酸钙或它们的混合物。
  8. 根据权利要求4-7中任何一项的方法，其中包膜材料经煅烧后成为下列中的一种：锐钛矿型TiO2，二氧化锡SnO2，金红石型TiO2，赤铁矿型Fe2O3，TiO2+FeO3，SnO2+TiO2+Fe2O3，SnO2+Fe2O3，钛和铁的混合氧化物，以及锡、钛、铁的混合氧化物。
  9. 由权利要求1-8中任何一项的方法所获得的珠光颜料。
  10. 权利要求9的珠光颜料的用途，它用于油漆、印刷油墨、塑料、陶瓷材料、皮革着色、壁纸、粉末涂料或化妆品领域。
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